Surface treatment of fluorinated contact lens materials

ABSTRACT

Hydrogen-plasma modification of a contact lens made from a fluorinated polymer reduces the surface chemistry of by removing fluorine, leaving behind a carbon-enriched surface that is further plasma processed into a hydrophilic surface for a lens material to be inserted into the ocular environment.

FIELD OF THE INVENTION

The present invention relates to a method for surface treating a fluorinated contact lens. The process comprises treating the lens with a hydrogen-containing plasma to reduce the fluorine content of the surface layer, followed by oxidation of the surface to increase its oxygen and/or nitrogen content, thereby improving its wettability or providing chemical functionality for subsequent processing.

BACKGROUND OF THE INVENTION

Contact lenses made from fluorinated materials have been investigated for a number of years. Such materials can generally be subdivided into two major classes, namely hydrogels and non-hydrogels. Non-hydrogels do not absorb appreciable amounts of water, whereas hydrogels can absorb and retain water in an equilibrium state. Regardless of their water content, both non-hydrogel and hydrogel fluorinated contact lenses tend to have relatively hydrophobic, non-wettable surfaces.

The art has recognized that introducing fluorine-containing groups into contact lens polymers can significantly increase oxygen permeability. For example, U.S. Pat. No. 4,996,275 to Ellis et al. discloses using a mixture of comonomers including the fluorinated compound bis(1,1,1,1,3,3,3-hexafluoro-2-propyl)itaconate in combination with organosiloxane components. As described in U.S. Pat. Nos. 4,954,587, 5,079,319 and 5,010,141, the fluorination of certain monomers used in the formation of silicone hydrogels has been indicated to reduce the accumulation of deposits on contact lenses made from such materials. Moreover, the use of silicone-containing monomers having certain fluorinated side groups, i.e. —(CF₂)—H, have been found to improve compatibility between the hydrophilic and silicone-containing monomeric units, as described in U.S. Pat. Nos. 5,387,662 and 5,321,108 to Kunzler et al. Other fluorinated contact lens materials have been disclosed, for example, in U.S. Pat. No. 3,389,012; U.S. Pat. No. 3,962,279; and U.S. Pat. No. 4,818,801.

Those skilled in the art have recognized the need for modifying the surface of fluorinated contact lenses so that they are compatible with the eye. It is known that increased hydrophilicity of a contact-lens surface improves the wettability of the contact lenses. This in turn is associated with improved wear comfort of the contact lens. Additionally, the surface chemistry of the lens can affect the lens's susceptibility to deposition, particularly the deposition of proteins and lipids from the tear fluid during lens wear. Accumulated deposition can cause eye discomfort or even inflammation. In the case of extended-wear lenses, the surface is especially important, since extended-wear lenses must be designed for high standards of comfort over an extended period of time, without requiring daily removal of the lenses before sleep. Thus, the regimen for the use of extended-wear lenses would not provide a daily period of time for the eye to rest or recover from any discomfort or other possible adverse effects of lens wear during the day.

Contact lenses have been subjected to plasma surface treatment to improve their surface properties, with the intent to render their surfaces more hydrophilic, deposit resistant, scratch resistant, or otherwise modified. For example, plasma treatment to effect better adherence of a subsequent coating is generally known. U.S. Pat. No. 4,217,038 to Letter discloses, prior to coating a silicone lens with sputtered silica glass, etching the surface of the lens with an oxygen plasma to improve the adherence of a subsequent coating. U.S. Pat. No. 4,096,315 to Kubacki discloses a three-step method for coating plastic substrates such as lenses, preferably PMMA (polymethylmethacrylate) lenses. The method comprises plasma treating the substrate to form hydroxyl groups on the substrate in order to allow for good adherence, followed by a second plasma treatment to form a silicon-containing coating on the substrate, followed finally by a third plasma treatment with inert gas, air, oxygen, or nitrogen. Kubacki states that pretreatment with hydrogen, oxygen, air or water vapor, the latter preferred, forms hydroxy groups. Neither Letter nor Kubacki discusses the surface treatment of fluorinated contact lens materials in particular.

U.S. Pat. No. 4,312,575 to Peyman teaches the use of hydrogen/fluorocarbon gaseous mixtures to treat silicone lenses. In Example 2 of Peyman, polydimethylsiloxane lenses are initially treated with a 50% hydrogen/50% tetrafluoroethylene mixture, followed by an oxygen plasma treatment. Peyman states that when it is desired to utilize a halogenated hydrocarbon to perform the plasma polymerization process, hydrogen gas may be added to the halogenated hydrocarbon in order to accelerate the polymerization reaction. In particular, Peyman states that hydrogen may be added to the plasma polymerization apparatus in an amount ranging from about 0.1 to about 5.0 volumes of hydrogen per volume of the halogenated hydrocarbon. Peyman does not mention how to surface treat fluorinated materials sucha s flourosilicon hydrogel or highly fluorinated contact lens materials.

U.S. Pat. No. 4,631,435 to Yanighara et al. discloses a plasma polymerization process employing a gas containing at least one compound selected from halogenated alkanes, alkanes, hydrogen and halogens in specific combinations, the atomic ratio of halogen/hydrogen in the aforesaid gas being 0.1 to 5 and the electron temperature of the plasma in the reaction zone being 6,000° K. to 30,000° K. The resulting coating is, in particular, suitable as the protective film for magnetic recording media.

U.S. Pat. Nos. 5,153,072; 5,091,204; 5,034,265; and 4,565,083 to Ratner disclose a method of treating articles to improve their biocompatibility according to which a substrate material is positioned within a reactor vessel and exposed to plasma gas discharge in the presence of an atmosphere of an inert gas such as argon and then in the presence of an organic gas such as a halocarbon or halohydrocarbon gas capable of forming a thin, biocompatible surface covalently bonded to the surface of the substrate. The method is particularly useful for the treatment of vascular graft materials. The graft material is subjected to plasma gas discharge at 5-100 watts energy. Ratner does not discuss the surface treatment of a fluorinated contact-lens materials.

In view of the above, it would be desirable to provide a fluorinated contact lens with an optically clear, hydrophilic surface film that will exhibit improved wettability and biocompatibility. It would be further desirable to be able to surface treat a fluorinated hydrogel or non-hydrogel contact lens that would allow its use in the human eye for an extended period of time. In particular, it would be desirable to provide a high-Dk fluorinated ophthalmic lens capable of extended wear for continous periods of at least 24 hours and, more preferably, to provide a biocompatible lens capable of continous and comfortable wear for 3 to 30 days without unacceptable corneal swelling or other adverse effects.

SUMMARY OF THE INVENTION

The invention relates to a method of treating a fluorinated contact lens comprising the following steps:

(a) treating the polymer surface of the lens with a hydrogen-containing plasma to reduce the fluorine or C—F bonding content of the lens; and

(b) plasma treating the reduced polymer surface with an oxidizing gas to increase its oxygen or nitrogen content.

This surface oxidation can improve the wettability or biocompatibility of the contact lens. Alternatively, the surface oxidation can provide chemical functionality for subsequent surface-modification processing such as the attachment of hydrophilic polymers (inclusive of oligomers or macromonomers) to the surface of the contact lens. The present invention is also directed to a contact lens that can be made by the above-described method.

DETAILED DESCRIPTION OF INVENTION

As indicated above, the present invention is directed to the surface treatment of a fluorinated contact lens material, preferably either a fluorinated silicone hydrogel material or a non-hydrogel material that is highly fluorinated. The hydrogen plasma treatment of a fluorine-containing material has been found to cause the loss of fluorination and/or C—F bonding over a surface depth of approximately 74 ångstroms into the material. The hydrogen (being present in excess) is also believed to fill radical sites on the polymer surface allowing chemical reduction of the polymer. Without wishing to be bound by theory, since the plasma gas-phase reactions on the surface of a material are complex, it is believed that typically the hydrogen reacts with fluorine at the surface of the lens, forming HF which can be carried off by a vacuum pump during the process. Thus, the invention utilizes a hydrogen-gas-containing plasma to reduce fluorinated surface chemistries. At the same time, the carbon content (as measured by XPS analysis) tends to increase, allowing improved oxidation in a subsequent plasma oxidation step.

In the case of fluorosilicone materials, the HF formed in the gas phase can be utilized to attack the silicone backbone of the polymer. The fluorine is believed to chemically react with the silicon atoms in the film, thereby forming SiF_(x) species. When such a species has four fluorine atoms (SiF₄), the molecule can be pumped off by the vacuum, causing the loss of silicon from the film. At the same time, the large excess in hydrogen molecules causes the addition of hydrogen to the remaining chemistry, the hydrogen further reducing the surface of the lens material. The hydrogen-reduced surface of the lens can then be further modified by the use of subsequent oxidizing plasmas.

The process conditions of the present invention may be substantially the same as those in conventional plasma polymerization. The degree of vacuum during plasma polymerization may be 1×10⁻³ to 1 torr and the flow rate of the gas flowing into the reactor may be, for example, 0.1 to 300 cc (STP)/min in the case of the reactor having an inner volume of about 100 liter. The above-mentioned hydrogen gas may be mixed with an inert gas such as argon, helium, xenon, neon or the like before or after being charged into the reactor. The addition of halogenated alkanes is unnecessary but not deleterious, and may be present in combination with the hydrogen, preferably at an atomic ratio of less than ten percent of gaseous halogen to hydrogen. The substrate temperature during plasma polymerization is not particularly limited, but is preferably between 0° and 300° C.

The type of discharge to be used for the generation of plasma is not particularly limited and may involve the use of DC discharge, low frequency discharge, high frequency discharge, corona discharge or microwave discharge. Also, the reaction device to be used for the plasma polymerization is not particularly limited. Therefore either an internal electrode system or an electrodeless system may be utilized. There is also no limitation with respect to the shape of the electrodes or coil, or to the structure or the cavity or antenna in the case of microwave discharge. Any suitable device for plasma polymerization, including known or conventional devices, can be utilized.

Preferably, the plasma is produced by passing an electrical discharge, usually at radio frequency, through a gas at low pressure (0.005-5.0 torr). Accordingly, the applied radio frequency power is absorbed by atoms and molecules in the gaseous state, and a circulating electrical field causes these excited atoms and molecules to collide with one another as well as the walls of the chamber and the surface of the material being treated. Electrical discharges produce ultraviolet (UV) radiation, in addition to energetic electrons and ions, atoms (ground and excited states), molecules and radicals. Thus, a plasma is a complex mixture of atoms and molecules in both ground and excited states which reach a steady state after the discharge is begun.

The effects of changing pressure and discharge power on the plasma treatment is generally known to the skilled artisan. The rate constant for plasma modification generally decreases as the pressure is increased. Thus, as pressure increases the value of E/P, the ratio of the electric field strength sustaining the plasma to the gas pressure, decreases and causes a decrease in the average electron energy. The decrease in electron energy in turn causes a reduction in the rate coefficient of all electron-molecule collision processes. A further consequence of an increase in pressure is a decrease in electron density. Taken together, the effect of an increase in pressure is to cause the rate coefficient to decrease. Providing that the pressure is held constant there should be a linear relationship between electron density and power. Thus, the rate coefficient should increase linearly with power.

Hydrogen plasmas have been found to reduce fluorination by attacking C—F bonds forming C—H bonds. In the present invention, the surface chemistry of the fluorinated material is reduced to allow for subsequent oxidation. Such a preliminary reduction was found necessary, in order to reduce or eliminate the delamination of the oxidized surface. While investigating the dynamics of the hydrogen plasma with fluorinated substrates, it was further discovered that the silicone backbone in fluorosilicone materials could be removed by action of the plasma. As mentioned above, it is believed that the hydrogen gas forms HF gas which attacks the silicone backbone, and this is believed to convert much or most of the polymer backbone at the surface to aliphatic carbon species, thus tending to increase the carbon content of the surface. The carbon formed contains a fair amount of stereoregularity, and this carbon structure has lattice vibrations similar to graphite, although some unsaturation was also detected through the use of X-ray Photoelectron Spectroscopy (XPS). A substantial part of the original C—F bonding can be removed by the hydrogen plasma modification. By the term “C—F bonding” is meant (as in Tables 8 and 9 in the examples below) the total C—F bonding, whether in —CF, —CF₂ or —CF₃ groups.

Thus, the fluorine or C—F bonding content is reduced by at least 25 percent, preferably at least 50 percent, over the first 74 angstroms of the surface as determined by XPS analysis. The present invention also covers a contact lens, which when in the unhydrated state as is the condition of XPS analysis, has a surface coating characterized by a fluorine or C—F bonding content within a depth of about 74 ångstroms that is at least 25 percent, preferably at least 50 percent, depleted relative to the bulk material.

The surface of the hydrogen-plasma-treated fluorinated material is further treated by oxidation, to increase its wettability or to provide chemical functionalites (reactive sites) for subsequent coating steps. Suitably, plasma oxidization is accomplished employing an oxygen or nitrogen-containing plasma. For example, the hydrogen-plasma chemically reduced surface can be oxidized by means of a plasma gas containing ammonia, air, water, peroxide, O₂ (oxygen gas), methanol, acetone, alkylamines, and the like or combinations thereof.

The oxidization of the surface results in an increase in the nitrogen and/or oxygen content by at least 5 percent over the first 74 ångstroms of the surface as determined by XPS analysis, before further processing of the lens such as extraction or heat sterilization. The present invention also covers a contact lens, which when in the unhydrated state as is the condition of XPS analysis, has a surface coating characterized by an oxygen content within a depth of about 74 ångstroms that is at least 2 mole percent enriched relative to the bulk material, based on XPS analysis.

The invention is applicable to a wide variety of fluorinated contact-lens materials. The fluorine content in the top 74 ångstroms of the surface, before or after treatment according to the present invention, can be measured by XPS analysis. See, for example, C. D. Wagner, W. M. Riggs, L. E. Davis, J. F. Moulder, Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer Physical Electronics Division, 6509 Flying Cloud Drive, Eden Prairie, Minn., 1978; D. M. Hercules, S. H. Hercules, “Analytical Chemistry of Surfaces, Part II. Electron Spectroscopy,” Journal of Chemical Education, 61, 6, 483, 1984; D. M. Hercules, S. H. Hercules, “Analytical Chemistry of Surfaces,” Journal of Chemical Education, 61, 5, 402, 1984, which are all hereby incorporated by reference. The determination of the depth of the analysis is based on the following equation:

KE=hν−BE−φ

wherein hν=1486.6 eV (electron Volts) is the energy of the photon (e.g., the x-ray energy of the A1 anode), KE is the kinetic energy of the emitted electrons detected by the spectrometer in the XPS analysis, and φ is the work function of the spectrometer. BE is the binding energy of an atomic orbital from which the electron originates and is particular for an element and the orbital of that element. For example, the binding energy of carbon (aliphatic carbon or CH_(x)) is 285.0 eV and the binding energy of fluorine (in a C—F bond) is 689.6 eV. Furthermore,

(KE)^(1/2)=λ

δ=3λ sin θ

wherein θ is the takeoff angle of the XPS measurement (e.g., 45°), δ is the depth sampled (approximately 74 ångströms, as in the examples below), and λ is the mean free path or escape depth of an electron. As a rule of thumb, 3λ is utilized to estimate sampling depth since this accounts for 95% of the signal originating from the sample.

As indicated above, the method of the present invention is applicable to fluorinated materials and is especially advantageous for the treatment of fluorosilione hydrogels and non-hydrogels made from highly fluorinated polymers. In general, hydrogels are a well known class of materials which comprise hydrated, cross-linked polymeric systems containing water in an equilibrium state. Non-hydrogels include elastomers and no-water or low-water xerogels. Fluorosilicone hydrogels generally have a water content greater than about 5 weight percent and more commonly between about 10 to about 80 weight percent. Fluorosilicone hydrogels (i.e., the bulk polymeric material from which it is composed) generally contains up to about 20 mole percent fluorine atoms and as low as about 1 mole percent fluorine atoms, which to some extent may become enriched near the surface, depending on the manufacturing process such as the hydrophobiciy of the lens mold. In one embodiment of the invention, the polymer material contains about 5 to 15 mole percent fluorine atoms, wherein the mole percents are based on the amounts and structural formula of the components in bulk of the fluorinated polymer making up the contact lens. Such materials are usually prepared by polymerizing a mixture containing at least one fluorinated silicone-containing monomer and at least one hydrophilic monomer. Typically, either the fluorosilicone monomer or the hydrophilic monomer functions as a crosslinking agent (a crosslinker being defined as a monomer having multiple polymerizable functionalities), or a separate crosslinker may be employed. Applicable fluorosilicone monomeric units for use in the formation of contact-lens hydrogels are well known in the art and numerous examples are provided in commonly assigned U.S. Pat. No. 5,321,108 to Kunzler et al. and U.S. Pat. No. 4,810,764, to Friends et al., which patents are hereby incorporated by reference in their entirety. The present invention is also applicable to the fluorinated materials (e.g., B-1 to B-14) in U.S. Pat. No. 5,760,100 to Nicholson et al.

Another class of fluorinated materials that can be treated by the present invention are highly fluorinated non-hydrogel materials. Highly fluorinated polymer materials have at least about 10 mole percent fluorine atoms, preferably about 20 to about 70 mole percent fluorine, again based on the amounts and structural formulae of the components of the polymer. Such materials include, for example, high-Dk fluoropolymeric rigid-gas-permeable contact-lens articles made from materials comprising perfluorinated monomers. An especially advantageous (high-Dk) material comprises an amorphous copolymer of perfluoro-2,2-dimethyl-1,3-dioxole with one or more copolymerizably acceptable ethylenically unsaturated fluorinated comonomers, the proportion of perfluoro-2,2-dimethyl-1,3-dioxole in the copolymer being at least about 20 mole percent of the copolymer. The latter contact-lens material may further comprise from 10 to 80 weight percent of one or more other comonomers, for example, selected from tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene (CTFE) vinylidene fluoride, perfluoro(alkyl vinyl) ether (PAVE) having the formula

CF₂—CFO(CF₂CFXO)_(n)R_(f) wherein X is F or CF₃,n is 0-5, and R_(f) is a perfluoroalkyl group of 1-6 carbon atoms, and mixtures thereof. Such monomers are disclosed in commonly assigned copending application Ser. No. 09/220,002 filed on even date herewith, the disclosure of which is hereby incorporated by reference in its entirety. Another class of highly fluorinated non-hydrogel materials are xerogels or elastomers, an example of which is disclosed in commonly assigned U.S. Pat. No. 5,714,557 to Kunzler and Ozark.

In one embodiment of the invention, a hydrogen-plasma treated fluorinated polymeric surface is subsequently oxidized by an oxidizing plasma, e.g., employing O₂ (oxygen gas), water, hydrogen peroxide, air, ammonia, etc., or mixtures thereof, creating radicals and oxidized functional groups. Such oxidation renders the surface of a lens more hydrophilic and wettable. Optionally further surface treatment can be carried out, for example, the attachment of hydrophilic polymers (including macromonomers and oligomers) as disclosed in the prior art. The attachment of polymers to chemical or reactive functionalities on the surface is disclosed, for example, in U.S. Pat. No. 5,805,264 to Janssen et al.; U.S. Pat. No. 5,260,093 to Kamel et al.; and U.S. Pat. No. 4,979,959 to Guire. Other patents or literature references teaching the attachment of hydrophilic polymers to the functionalized surface of a material will be known to the skilled artisan.

In practice, contact lenses may be surface treated by placing them, in their unhydrated state, within an electric glow discharge reaction vessel (e.g., a vacuum chamber). Such reaction vessels are commercially available. The lenses may be supported within the vessel on an aluminum tray (which acts as an electrode) or with other support devices designed to adjust the position of the lenses. The use of specialized support devices which permit the surface treatment of both sides of a lens are known in the art and may be used in the present invention.

The plasma treatment, for example hydrogen or hydrogen in an inert gas such as argon, may suitably utilize an electric discharge frequency of, for example, 13.56 MHz, suitably between about 100-1000 watts, preferably 200 to 800 watts, more preferably 300 to 500 watts, at a pressure of about 0.1-1.0 torr. The plasma-treatment time is preferably at least 2 minutes total, and most preferred at least 5 minutes total. Optionally, the lens may be flipped over to better treat both sides of the lens. The plasma-treatment gas is suitably provided at a flow rate of 50 to 500 sccm (standard cubic centimeters per minute), more preferably 100 to 300 sccm. The thickness of the surface treatment is sensitive to plasma flow rate and chamber temperature, as will be understood by the skilled artisan. Since the coating is dependent on a number of variables, the optimal variables for obtaining the desired or optimal coating may require some adjustment. If one parameter is adjusted, a compensatory adjustment of one or more other parameters may be appropriate, so that some routine trial and error experiments and iterations thereof may be necessary in order to achieved the coating according to the present invention. However, such adjustment of process parameters, in light of the present disclosure and the state of the art in plasma treatment, should not involve undue experimentation. As indicated above, general relationships among process parameters are known by the skilled artisan, and the art of plasma treatment has become well developed in recent years. The Examples below provide the Applicants' best mode for forming the coating on fluorinated lenses.

The present invention is especially advantageous with respect to a contact lens for extended-wear or specialty uses, such as for relatively thick lenses. Extended lenses are lenses capable of being worn overnight, preferably capable of being worn for at least one week, most preferably capable of wear for a continuous period of one week to one month. By “capable” is meant lenses approved by one or more governmental regulatory authorities for such consumer use, for example, the U.S. Food & Drug Administration (USFDA) in the US or its equivalent in other countries.

Extended-wear lenses require relatively high oxygen permeability. The oxygen-permeability is the rate at which oxygen will pass through a material. The oxygen-permeability Dk of a lens material does not depend on lens thickness. Oxygen permeability is measured in terms of barrers which have the following units of measurement:

((cm³ oxygen)(mm)/(cm²)(sec)(mm Hg))×10⁻¹⁰

or, alternatively,

((cm³ oxygen)(cm)/ (cm²)(sec)(mm Hg))×10⁻¹¹

On the other hand, the oxygen transmissibility of a lens, as used herein, is the rate at which oxygen will pass through a specific lens. Oxygen transmissibility, Dk/t, is conventionally expressed in units of barrers/mm, where t is the average thickness of the material (in units of mm) over the area being measured. For example, a lens having a Dk of 90 barrers (oxygen-permeability barrers) and a thickness of 90 microns (0.090 mm) would have a Dk/t or 100 barrers/mm (oxygen transmissibility barrers/mm).

The fluorinated materials of the present invention suitably have an oxygen permeability (Dk) that is suitably greater than 70 barrers, preferably greater than 100 barrers, for example 100 to 200 barrers, or in the case of some perfluorinated materials, as high as 200 to 500 barrers.

The examples which follow are illustrative of specific embodiments of the invention, and various uses thereof. They set forth for explanatory purposes only, and are not to be taken as limiting the invention.

EXAMPLE 1

This example illustrates the surface chemical effects of treating a fluoro gel material according to the present invention with a hydrogen plasma. The fluorogel material is made according to U.S. Pat. No. 5,321,108 to Kunzler et al., in particular the 40/10/10/10 mixture of 25 mole % octafluorosilicone/TRIS/DMA/NVP in Table 3 of the patent. As shown by the following series of experiments, the net effect of a hydrogen plasma can be oxidizing or reducing, depending on the conditions utilized in the processing window. By choosing the conditions for a reducing plasma, a surface can be created that allows for the addition of ammonia to create net increases in —NH₂ functionality (+14% atomic concentration as determined by XPS) at the surface, with associated reductions in —CF₂. The amount of NH₂ on the surface was subsequently reduced by extraction and autoclaving after plasma treatment (+6% atomic concentration as determined by XPS). However, substantial amounts of the treatment remain after full processing of the lens.

The plasma chamber was a direct current DC Radio Frequency Glow Discharge (RFGD) chamber manufactured by (Metroline Model 7102). This chamber is a cold equilibrium planar configuration with a discharge at 13.56 MHz that has a maximum power of 1000 watts. All samples were pre-pumped to 0.01 torr prior to any introduction of working gas. All working gases were allowed to equilibrate for a period of 2 to 5 minutes including between subsequent steps.

The X-ray Photoelectron Spectrometer (XPS) utilized in this study was a Physical Electronics [PHI] Model 5600. This instrument utilized an aluminum anode operated at 300 watts, 15 kV and 27 milliamps. The excitation source was monochromatized utilizing a torodial lens system. The 7 mm filament was utilized for the polymer analysis due to the reduced sample damage and ease of photoionization neutralization. The base pressure of this instrument was 2.0×10⁻¹⁰ torr while the pressure during operation was 1.0×10⁻⁹ torr. This instrument made use of a hemispherical energy analyzer. The practical measure of sampling depth for this instrument at a sampling angle of 45° and with respect to carbon was approximately 74 angstroms (see calculations below). All elements were charge corrected to the CH_(x) peak of carbon to a binding energy of 285.0 electron volts (eV).

Each of the specimens was analyzed utilizing a low resolution survey spectra [0-1100 eV] to identify the elements present on the sample surface. The high resolution spectra were performed on those elements detected from the low resolution scans. The elemental composition was determined from the high resolution spectra. The atomic composition was calculated from the areas under the photoelectron peaks after sensitizing those areas with the instrumental transmission function and atomic cross sections for the orbital of interest. Since XPS does not detect the presence of hydrogen or helium, these elements will not be included in any calculation of atomic percentages. It is also noted that atomic percentages may vary if a different instrument design, i.e. transmission function, is utilized, so that for purposes of exact reproducibility the atomic percentage numbers in the application refer to the specified instrument design, as will be understood by the skilled artisan.

The low resolution XPS survey spectra taken at a takeoff angle of 45 degrees for the untreated fluoroxerogel surfaces contained peaks for fluorine, carbon, oxygen and silicon. The analysis of the fluorogel material begins with the examination of the unmodified matrix (control). Table 1 below contains the XPS data for the hydrogen plasma modification of fluorogels. This data reflects the atomic composition over the top 74 ångstroms (relative to carbon 1s electrons). The percentages reflect all elements except hydrogen, helium, and free lithium. As indicated in Table 1, the low resolution survey spectra of the control (Sample 1) polymer contained peaks for fluorine (10%), oxygen (14%), nitrogen (1%), carbon (67%) and silicon (7%). The initial plasma modifications of this material with hydrogen attempted to remove fluorine and chemically reduce the rest of the matrix. In this embodiment of the invention, the idea was to reduce chemical sites on the surface for future oxidation by ammonia. The method chosen to accomplish this was to start with mild plasma excitation conditions and move towards more aggressive plasma environments (varying pressure and wattage). Initially a 50 watt, 0.5 torr, 10 minute plasma was performed in a hydrogen environment. This plasma resulted in the reduction of the fluorine content (Sample 2 in Table 1). The reduction in fluorine was accompanied by a slight increase in oxygen and silicon. The increased silicon and oxygen concentrations were the result of a slight oxidation of the silicon to a silicate. The next set of plasma conditions increase the strength of the field: 100 watt, 0.5 torr for 5 minutes (Sample 3 in Table 1). The reduction in time was an attempt to create approximately the same treatment at more aggressive wattage conditions and to examine the net effect on oxidation. The result was surprising in that the fluorine content decreased while the silicon and oxygen levels remained constant. Thus, the carbon content increased from the removal of the fluorine (initially 10% and 4.5% after this plasma). Increasing the time to 10 minutes (for 100 watt, 0.5 torr) resulted in increased oxidation of the substrate that increased the amount of oxygen and silicon. Further wattage and pressure increases resulted in the further oxidation of the substrate while also reducing the effectiveness of the defluorination process. This can be seen in Table 1, where the pressure increases to 1.0 torr and wattage increases to 300 and 500 watts were examined. These experiments were all performed at ten minutes to have a basis of comparison. Due to the increases in the oxidation of the matrix by increased wattage plasma, it was determined that the 100 watt, 5 minute, 0.5 torr would represent the best reduction of surface chemistry for subsequent oxidation for this material in this embodiment of the invention.

The next series of experiments examined the effects of the two-stage plasma treatment. Table 2 below contains the XPS data for the combined hydrogen and ammonia plasma modification of the fluorogel material. The data in the Table reflects the atomic composition (by XPS analysis) over the top 74 ångstroms (relative to carbon 1s electrons). As shown in Table 2, the initial reduction plasma made use of the 50 watt, 5 minute, 0.5 torr hydrogen-gas plasma discussed above. The chemically-reduced fluorogel surface was then subsequently exposed to an oxidizing plasma of ammonia. The most successful plasmas were composed of low wattage and pressure at extended periods of time, and therefore the experimental plasma conditions consisted of 100 watts, 0.5 torr, for a period of 15 minutes. As shown in Table 2 below, this plasma resulted in the incorporation of 15% nitrogen into the reduced fluorogel polymer in the form of an amine. This plasma also increased the amount of fluorine present while reducing the overall carbon levels. The plasma-oxidized product was then sent to processing and autoclave sterilization. As indicated in Table 2, the net effect of the extraction and the autoclaving was the reduction in the net nitrogen by about 50% (7.5%). In addition, increases in the amount of oxygen present were also found. The oxygen concentration increases were believed to be from the hydrolysis of the Si—F bounds formed in the second part of the plasma. The resulting fully-processed fluorogel polymer exhibited a 35 degree water contact angle while dry.

TABLE 1 Process Sample Description Oxygen Carbon Fluorine Nitrogen Silicon N/C O/C 1 Control Average 14.4 67.1 10.2  1.4 6.9  0.02  0.21 ST DEV  1.1  0.9 0.3 0.2 0.1 0.0 0.0 2 H₂/50 Watts/ Average 18.6 65.6 5.1 1.2 9.9 0.0 0.3 10 Min/0.5 Torr ST DEV  0.9  1.1 0.2 0.3 0.2 0.0 0.0 3 H₂/100 Watts/ Average 15.6 71.6 4.5 0.9 7.3 0.0 0.2 5 Min/0.5 Torr ST DEV  3.2  5.3 0.2 0.6 1.8 0.0 0.1 4 H₂/100 Watts/ Average 16.6 69.9 5.0 1.2 7.7 0.0 0.2 10 Min/0.5 Torr ST DEV  0.6  2.4 1.0 1.2 0.2 0.0 0.0 5 H₂/300 Watts/ Average 13.8 71.9 6.8 4.7 2.8 0.1 0.2 10 Min/0.5 Torr ST DEV  0.3  1.9 0.4 0.8 0.4 0.0 0.0 6 H₂/500 Watts/ Average 15.7 64.1 11.6  4.4 4.2 0.1 0.2 10 Min/0.5 Torr ST DEV  0.5  0.1 0.7 0.2 0.1 0.0 0.0 7 H₂/500 Watts/ Average 30.8 46.6 8.2 1.9 12.5  0.0 0.7 10 Min/1 Torr ST DEV  1.0  1.8 0.1 0.1 0.8 0.0 0.0 8 H₂/500 Watts/ Average 25.5 47.1 9.8 1.9 15.6  0.0 0.5 10 Min/0.25 Torr ST DEV  0.4  1.6 0.4 0.3 0.6 0.0 0.0

TABLE 2 Process Sample Description Oxygen Carbon Fluorine Nitrogen Silicon N/C O/C  9 Control Average 14.40 67.10 10.20  1.40  6.90 0.0 0.2 ST DEV 1.1 0.9 0.3 0.2 0.1 0.0 0.0 10 H₂/100 Watts/ Average 15.6  48.3  14.2  15.8  6.2 0.3 0.3 5 Min/0.5 Torr NH₃/100 Watts/ ST DEV 0.9 0.9 0.6 0.5 0.7 0.0 0.0 15 Min/0.5 Torr 11 H₂/100 Watts/ Average 26.3  52.8  3.3 7.9 9.7 0.2 0.5 5 Min/0.5 Torr ST DEV 0.3 2.3 1.2 0.7 0.8 0.0 0.0 NH₃/100 Watts/ 15 Min/1.0 Torr 12 Same as Sample Average 20.7  55.3  9.3 7.5 7.2 0.1 0.4 11 but also with ST DEV 2.3 5.4 1.2 0.3 2.1 0.0 0.1 alcohol extraction and autoclavving

EXAMPLE 2

This example illustrates the plasma treatment of another fluorinated contact-lens material according to the present invention. The material in this case was a fluoroxerogel. A xerogel is a material that contains less than two percent water. The fluorogel comprised the reacrion product of methacrylate end capped DP100 poly(65 mole %)methyl trifluoropropyl(35 mole %) dimethyl siloxane (“65 TFP”); octafluoropentyl methacrylate (“OFPMA”); and 3-methacryloxy propyl-1-propyloxyoctafluoro pentyl tetramethyl disiloxane (“MO”). See Example III in U.S. Pat. No. 5,714,557 to Kunzler and Ozark, hereby incorporated by reference.

A hydrogen-containing plasma was employed to reduce the fluorinated surface, after which it was oxidized. The first step was to examine the conditions necessary to maximize the reduction in the surface. The following experiments start at low wattage in an attempt to find the best E/P and then move up and through the energetically acceptable region. These initial tests utilized XPS to examine the surface chemistry of the films after modification.

Sample specimens were in the form of rectangular films which were extracted in toluene overnight and dried in a vacuum oven. The films were placed in plastic bags. The plasma chamber was a direct current DC Radio Frequency Glow Discharge (RFGD) chamber manufactured by (Branson Model 4155). This chamber is a cold equilibrium planar configuration with a discharge at 13.56 MHz that has a maximum power of 500 watts. All samples were pre-pumped to 0.01 torr prior to any introduction of working gas. All working gases were allowed to equilibrate for a period of 2 to 5 minutes including between subsequent steps. The X-ray Photoelectron Spectrometer (XPS) utilized in this study was a Physical Electronics [PHI] Model 5600. This instrument utilized an aluminum anode operated at 300 watts, 15 kV and 27 milliamps. The excitation source was monochromatized utilizing a torodial lens system. The 7 mm filament was utilized for the polymer analysis due to the reduced sample damage and ease of photoionization neutralization. The base pressure of this instrument was 2.0×10⁻¹⁰ torr while the pressure during operation was 1.0×10⁻⁹ torr. This instrument made use of a hemispherical energy analyzer. The practical measure of sampling depth for this instrument at a sampling angle of 45° and, with respect to carbon, was approximately 74 ångstroms. All elements were charge corrected to the CH_(x) peak of carbon to a binding energy of 285.0 electron volts (eV).

Each of the specimens was analyzed utilizing a low resolution survey spectra [0-1100 eV] to identify the elements present on the sample surface. The high resolution spectra were performed on those elements detected from the low resolution scans. The elemental composition was determined from the high resolution spectra. The atomic composition was calculated from the areas under the photoelectron peaks after sensitizing those areas with the instrumental transmission function and atomic cross sections for the orbital of interest. Since XPS does not detect the presence of hydrogen or helium, these elements will not be included in any calculation of atomic percentages.

The low resolution XPS survey spectra taken at a takeoff angle of 45 degrees for the untreated fluoroxerogel surfaces contained peaks for fluorine, carbon, oxygen and silicon. The carbon “1s” region was curve fit for the various carbon chemistries seen under the “1s” envelope. This procedure involved first fitting the carbon “1s” region with a peak for the CH_(x) carbon at 285.0 eV. This peak was fit by matching the qualitative structure of low binding energy side of the carbon “1s” peak which was exclusively due to CH_(x) carbon (assuming no graphite, carbides or diamond structure). The full width at half maximum (FWHM) value was adjusted along with the percentage Gaussian-Lorentzian peak shape. The FWHM and Gaussian-Lorentzian values for the CHx peak were utilized for all other peak shapes fit for a particular carbon “1s” envelope. The envelope was then fit with peaks at 286.5 eV for C—O bonding, 288.0 eV for C═O bonding, 289.0 eV for O═C—O bonding, 289.5 eV for C—F bonding, 292 eV for C—F₂ bonding and 292.8 eV for C—F₃. The computer was utilized to vary position and FWHM by +0.1 eV and to vary the percentage Gaussian-Lorentzian by five percent. The computer attempts different fits by varying position, FWHM and Gaussian-Lorentzian shape while measuring the residual of the attempted fit. The resultant carbon chemistries fit into the envelope are summarized in Table 3 below, along with the atomic concentration data, in an an attempt to understand the film behavior within 74 ångstroms.

TABLE 3 Specimen Fluorine Oxygen Carbon Silicon CHx C—Os CFs 1 28.19 14.46 47.65  9.70 58.36 25.25 18.49 2 28.46 14.22 47.19 10.42 63.64 18.71 17.65 3 28.08 15.27 45.98 10.67 64.69 19.60 15.71 4 27.42 14.97 46.46 11.14 65.04 19.23 15.73 5 28.59 13.87 48.14  9.39 59.28 22.45 18.26 6 27.75 14.35 47.48 10.42 — — — 7 26.90 14.84 47.39 10.87 — — — 8 26.57 14.49 47.73 11.22 — — — 9 26.52 14.61 47.80 11.07 — — — 10  27.97 14.71 47.66  9.66 — — — Average 27.6  14.6  47.3  10.5  62.2  21.0  17.2  ST DEV 0.8 0.4 0.7 0.7 3.1 2.8 1.4

For the hydrogen-plasma treatment of the polymer films, initially mild conditions were chosen: 25 watts, 0.5 torr pressure of hydrogen, for five minutes on a dacron mesh tray. This plasma was not very effective. There was only minor variations in polymer chemistry after plasma treatment at 25 watts as shown in Table 4 below. The second step examined an increase in time to ten minutes while maintaining the pressure and wattage. This had little to no effect on the polymer surface as shown in Table 5 below. Thus, the wattage was increased to increase the hydrogen molecular energies while maintaining pressure and time, as noted earlier. The power was increased to 50 watts as indicated in Table 6 below. This had a dramatic effect on the polymer surface chemistry. The flourine content of the surface dropped from around 28% to 6%. At the same time the oxygen content increased from approximately 15% to 27%, carbon content increased from 47 to 56% and the silicon content stayed about the same. It was most interesting to note the carbon “1s” curve fits revealed that the C—F bonding had decreased from 17% of the carbon envelope to 2.3%. This indicated that a majority of fluorine present in the film after plasma was in an ionic form and possibly HF and, therefore, should leave the polymer with processing.

TABLE 4 (5 min at 25 W) Trial Fluorine Oxygen Carbon Silicon 1 28.38 15.03 45.41  8.20 2 29.16 15.86 44.81 10.17 3 26.50 15.12 48.49 11.18 Average 28.0  15.3  46.2  9.9 ST DEV 1.4 0.5 2.0 1.5

TABLE 5 (10 min at 25W) Trial Fluorine Oxygen Carbon Silicon 4 30.41 14.81 46.58  8.20 5 34.08 15.5  43.68  7.11 6 28.90 15.12 43.11 12.48 Average 31.1  15.1  44.5  9.3 ST DEV 2.7 0.4 1.9 2.8

TABLE 6 (10 min at 50 W) Trial Fluorine Oxygen Carbon Silicon CHx C—Os CFs 7 6.51 28.33 52.86 12.30 86.87 10.79 2.33 8 7.02 27.85 53.13 12.00 85.90 11.91 2.20 9 4.22 23.18 62.91  9.70 87.90  9.76 2.34 Average 5.9  26.5  56.3  11.3  86.90 10.8  2.3  ST DEV 1.5  2.8 5.7 1.4 1.0 1.1 0.1 

Increasing the wattage further was found to reduce the polymer chemistry to an even greater extent. However, the reduction in chemistry was not excluded to the fluorine chemistry alone anymore. In fact, the hydrogen plasma appeared at higher wattages and times to reduce all chemistries present on the surface. This can be seen in the atomic concentration and carbon “1s” curve fit data in Tables 7 to 9 below. The data for the 100 watt, 300 watt, five and ten minute treatments can be examined as a sequential trend. The fluorine atomic percentage stays around 6% while the C—F bonding fluctuates towards 0%. The oxygen (15 to 27%) and silicon atomic percentage decrease (silicon from 11% to 5.2%). The silicon bonding energy was indicating Na₂SiF₆ at 104.2 eV. It may be that silicon was lost via the gas phase though the creation of SiF₄ (which should also be at 104.2 eV). This may account for some of the fluorine in the polymer not being present as C—F or F—H⁺. In addition, the carbon “1s” envelope is approximately 90% CHx type of chemistry. It is believed that the reduction in these chemistries may be the result of the formation of HF. At certain energies, this complex appears to attack the base polymer leaving primarily carbon behind. In addition, the carbon “1s” spectra has a long flat asymmetric tail reminiscent of a plasmon loss feature. A plasmon in XPS spectra is a loss in energy to the lattice vibrations in highly structured carbon atoms like graphite, diamond-like carbon and diamond. Further reductions in the silicon content appear. By raising the average particle energy and interaction time of time it was possible to get silicon contents as low as 5.2% on average (from an initial of 11%). The carbon content of this treated surface increased to 72% on average (from an initial value of 47%).

TABLE 7 (10 min at 100 W) Trial Fluorine Oxygen Carbon Silicon CHx C—Os CFs 10 6.41 23.03 61.63 8.94 76.36 22.52 1.14 11 6.15 24.79 59.18 9.88 87.80 10.80 1.31 12 8.58 24.14 59.19 8.09 87.61 10.49 1.90 Average 7.0  24.0  60.0  9.0  83.9  14.6  1.5  ST DEV 1.3  0.9 1.4 0.9  6.6 6.9 0.4 

TABLE 8 (5 min at 300 W) Trial Fluorine Oxygen Carbon Silicon CHx C—Os CFs 13 5.31 21.44 64.49 8.77 93.48  6.52 0   14 5.37 19.62 66.79 8.22 87.97 12.03 0   15 0.00 20.43 66.15 7.60 84.32 15.33 0.38 16 5.11 18.11 69.55 7.23 88.9  10.07 1.03 Average 3.9  19.9  66.7  8.0  88.7  11.0  0.4  ST DEV 2.6  1.4 2.1 0.7  3.8 3.7 0.5 

TABLE 9 (10 min at 300 W) Trial Fluorine Oxygen Carbon Silicon CHx C—Os CFs 17 6.77 18.80 68.40 6.03 88.04 10.76 1.2 18 5.96 15.03 74.67 4.34 86.63 11.59  1.78 19 6.12 17.12 71.68 5.27 87.86 10.73  1.40 Average 6.3  17.0  71.6  5.2  87.5  11.0  1.5 ST DEV 0.4  1.9 3.1 0.8  0.8 0.5 0.3

Following hydrogen-containing plasma treatment to reduce fluorinated surface chemistries, the polymer surface was oxidized. Again, these tests utilized XPS, as described in the above examples, to examine the surface chemistry of the films after modification. In particular, an ammonia-containing gas was selected in this example for oxidation of the hydrogen-plasma modified fluoroxerogel, in which the initial plasma was hydrogen at 200 watts and 300 watts for ten minutes at 0.5 torr. The results of the second plasma treatments are summarized in Table 10 and 11 below. The low resolution survey spectra of these specimens contained carbon, oxygen, nitrogen, fluorine and silicon. The atomic concentrations of oxygen (8%-16% after) and nitrogen (0.5%-11% after) was found to increase after treatment with ammonia for the 200 watt plasma only. This gave the 200 watt plasma treated material a water wettability of seven degrees following the oxidation. Therefore, the efficacy of the plasma treatment may require testing at a sequence of wattage or other process conditions to obtain satisfactory or optimal results.

TABLE 10 (at 45° at 300 W) Trial Fluorine Oxygen Nitrogen Carbon Silicon 20 8.54 6.79 0.80 81.82 2.06 21 6.74 6.89 0.00 85.08 1.28 22 7.50 6.07 0.67 84.67 1.10 23 8.06 7.03 0.48 82.56 1.88 24 7.67 6.57 0.11 84.60 1.05 Average 7.7  6.7  0.4  83.7  1.5  ST DEV 0.7  0.4  0.3  1.5 0.5 

TABLE 11 (at 45° at 200 W) Trial Fluorine Oxygen Nitrogen Carbon Silicon 25 9.61 15.41 10.17 61.56 3.26 26 9.29 13.35 11.74 62.97 2.66 27 8.90 14.25 10.05 63.62 3.18 28 9.93 12.84 11.90 63.19 2.15 Average 9.4  14.0  10.1  62.8  2.8  ST DEV 0.4  1.1 0.9 0.9 0.5 

EXAMPLE 3

This example illustrates the plasma treatment of another fluorinated contact-lens material according to the present invention, in this case a high-Dk fluoropolymeric lenses. The lenses were made from molded rods of a material obtained from Random Technologies (San Franciso, Calif.), which consisted of Teflon® AF 1600, comprising 65 mole percent PDD and 45 mole percent TFE, supplied by DuPont. The rods' dimensions were 12.7 mm diameter and 4 mm thick. Buttons were cut from the rods and lathed into contact lenses by techniques well known in the art. The resulting contact lenses were plasma treated as follows: The lenses were placed concave side up on an aluminum coated tray and the tray placed into a plasma treatment chamber. The plasma treatment chamber was a direct current DC RFGD chamber manufactured by Branson GaSonics Division (Model 7104). This chamber was a cold equilibrium planar configuration which had a maximum power of 1000 watts. All lenses were prepumped to 0.01 torr prior to any plasma treatment from residual air in the chamber. This process reduced the relative treatment level of the polymer by controlling gas pressure. The lens was first treated by passing hydrogen gas at 50 sccm into the chamber. The lenses were plasma treated for a period of 10 minutes (300 watts, 0.3 torr). Subsequently, the lenses were treated by passing 250 sccm air at into the chamber while plasma treating the lenses for a period of 5 minutes (100 watts, 0.3 torr). The contact angle of the lens with water (HPLC grade H₂O, 72.4 dynes/cm) was, before the plasma treatment, 115 degrees and, after the plasma treatment, was 0 degrees

Many other modifications and variations of the present invention are possible in light of the teachings herein. It is therefore understood that, within the scope of the claims, the present invention can be practiced other than as herein specifically described. 

What is claimed is:
 1. A fluorinated contact lens made by a process comprising the following steps: (a) plasma treating the fluorinated contact lens with a hydrogen-containing atmosphere for a total time period of at least 2 minutes, at a wattage of greater than 25 watts and a pressure of 0.1 to 1.0 torr, to reduce the fluorine content by at least 25 percent over the first 74 ångstroms of the surface as determined by x-ray photoelectron spectroscopy (XPS) analysis; and subsequently (b) oxidizing the surface wit an oxygen or nitrogen-containing gas or gaseous mixture.
 2. A fluorinated contact lens containing a fluorinated bulk material and a plasma treated surface, which when the lens is in the unhydrated state, is characterized by a fluorine content or a C—F bonding content within a depth of about 74 ångstroms that is at least 25 percent depleted relative to the bulk material, and an oxygen or nitrogen content within a depth of about 74 ångstroms that is at least 2 percent enriched relative to the bulk material, as determined by x-ray photoelectron spectroscopy (XPS) analysis, which enriched oxygen or nitrogen content provides the contact lens surface with improved wettability or biocompatibility.
 3. The lens of claim 2, wherein the fluorinated contact lens material is the polymerization product of a mixture comprising a fluorine-containing silicone monomer.
 4. The lens of claim 2, wherein the bulk contact lens material has an oxygen permeability (Dk) that is greater than 100 barrers. 